WO2011105490A1 - Corps fritté en carbure de silicium et composant de glissement l'utilisant, et corps protecteur - Google Patents

Corps fritté en carbure de silicium et composant de glissement l'utilisant, et corps protecteur Download PDF

Info

Publication number
WO2011105490A1
WO2011105490A1 PCT/JP2011/054150 JP2011054150W WO2011105490A1 WO 2011105490 A1 WO2011105490 A1 WO 2011105490A1 JP 2011054150 W JP2011054150 W JP 2011054150W WO 2011105490 A1 WO2011105490 A1 WO 2011105490A1
Authority
WO
WIPO (PCT)
Prior art keywords
silicon carbide
sintered body
graphite
sliding
carbide particles
Prior art date
Application number
PCT/JP2011/054150
Other languages
English (en)
Japanese (ja)
Inventor
真美 鈴木
美恵子 八嶋
石峯　裕作
和洋 石川
Original Assignee
京セラ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 京セラ株式会社 filed Critical 京セラ株式会社
Priority to US13/581,171 priority Critical patent/US9388083B2/en
Priority to JP2012501846A priority patent/JP5597693B2/ja
Priority to EP11747450.2A priority patent/EP2540688B1/fr
Priority to CN201180010704.1A priority patent/CN102770394B/zh
Publication of WO2011105490A1 publication Critical patent/WO2011105490A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62695—Granulation or pelletising
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/638—Removal thereof
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
    • F16C33/30—Parts of ball or roller bearings
    • F16C33/58—Raceways; Race rings
    • F16C33/62—Selection of substances
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J15/00—Sealings
    • F16J15/16—Sealings between relatively-moving surfaces
    • F16J15/34—Sealings between relatively-moving surfaces with slip-ring pressed against a more or less radial face on one member
    • F16J15/3496—Sealings between relatively-moving surfaces with slip-ring pressed against a more or less radial face on one member use of special materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3817—Carbides
    • C04B2235/3821—Boron carbides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422—Carbon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422—Carbon
    • C04B2235/424—Carbon black
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422—Carbon
    • C04B2235/425—Graphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5296—Constituents or additives characterised by their shapes with a defined aspect ratio, e.g. indicating sphericity
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/782—Grain size distributions
    • C04B2235/783—Bimodal, multi-modal or multi-fractional
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/786—Micrometer sized grains, i.e. from 1 to 100 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/788—Aspect ratio of the grains
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/963—Surface properties, e.g. surface roughness
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C2206/00—Materials with ceramics, cermets, hard carbon or similar non-metallic hard materials as main constituents
    • F16C2206/40—Ceramics, e.g. carbides, nitrides, oxides, borides of a metal
    • F16C2206/56—Ceramics, e.g. carbides, nitrides, oxides, borides of a metal based on ceramic carbides, e.g. silicon carbide (SiC)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y10T428/24372—Particulate matter
    • Y10T428/24421—Silicon containing

Definitions

  • the present invention relates to a silicon carbide sintered body, a sliding part using the same, and a protective body.
  • Silicon carbide-based sintered bodies are suitably used for sliding parts because they have high hardness and high corrosion resistance, and have a low coefficient of friction during sliding and excellent smoothness.
  • Patent Document 1 proposes a silicon carbide sintered body composed of at least one silicon carbide crystal phase of an ⁇ phase or ⁇ phase and a YAG crystal phase, and the balance being inevitable impurities.
  • a silicon carbide sintered body in which the average crystal particle diameter of silicon carbide in the sintered body is 3 ⁇ m or less and the average crystal particle diameter of YAG crystals is 1 ⁇ m or less is described as a preferred example. ing.
  • the silicon carbide sintered body proposed in Patent Document 1 is substantially dense without pores and excellent in strength and hardness, a low-strength YAG crystal phase is also included in the grain boundary phase. If the silicon carbide sintered body is subjected to a thermal shock applied to the sliding surface when used as a sliding part, cracks are likely to occur and the cracks are likely to propagate through the grain boundary phase, and the It could not withstand enough use. Recently, the use of a silicon carbide sintered body as a protective body has been studied, and a silicon carbide sintered body in which cracks do not easily progress is desired.
  • the present invention has been devised to solve the above-described problems, and even if a fine crack is generated due to a thermal shock or a mechanical shock that is received over a long period of time, the development of the crack can be suppressed. It is an object of the present invention to provide a silicon carbide sintered body that can be produced, a sliding component using the same, and a protective body.
  • the silicon carbide based sintered body of the present invention is a silicon carbide based sintered body mainly composed of silicon carbide particles and having a relative density of 95% or more, and has an area of 170 ⁇ m on the observation surface of the silicon carbide based sintered body. Two or more coarse granular silicon carbide particles are present in the range of 6 to 15 area%.
  • the sliding component of the present invention is characterized by polishing the surface of the silicon carbide sintered body of the present invention having the above-described configuration.
  • the protective body of the present invention is characterized by using the silicon carbide sintered body of the present invention having the above-described configuration.
  • the silicon carbide-based sintered body of the present invention is mainly composed of silicon carbide particles and has a relative density of 95% or more.
  • Coarse granular silicon carbide particles having a particle size of 170 ⁇ m 2 or more exist in an area of 6 to 15 area%, so that even if fine cracks are generated due to thermal shock or mechanical shock, the coarse granular silicon carbide particles cause the cracks to progress. Since it can suppress, it can be set as the silicon carbide sintered body excellent in thermal shock resistance with mechanical characteristics, such as intensity
  • the sliding component of the present invention since the surface of the silicon carbide sintered body of the present invention is polished, by the effect of suppressing the progress of cracks when a fine crack is generated by thermal shock, Along with excellent mechanical properties such as strength and rigidity, and excellent thermal shock resistance, it can withstand long-term use as a sliding component.
  • the silicon carbide sintered body of the present invention since the silicon carbide sintered body of the present invention is used, the effect of suppressing the progress of cracks when a fine crack is generated by mechanical impact, the strength, rigidity Therefore, it can be suitably used as a protective body.
  • (A), (b) is a microscope picture in the observation surface of the silicon carbide sintered body of this embodiment. It is a schematic diagram which shows an example of the crystal structure of a graphite.
  • An example of the mechanical seal provided with the sliding component of this embodiment is shown, (a) is a partial cross-sectional view, and (b) is a perspective view of the mechanical seal ring shown in (a).
  • An example of the forceset valve provided with the sliding component of this embodiment is shown, (a) is a perspective view of a state where the fluid passage is opened, and (b) is a perspective view of a state where the fluid passage is closed.
  • the rolling bearing which is an example of the rolling support apparatus provided with the sliding component of this embodiment is shown, (a) is sectional drawing, (b) is a perspective view which shows the holder of the rolling bearing shown to (a). is there.
  • FIGS. 1A and 1B are micrographs on the observation surface of the silicon carbide based sintered body of the present embodiment.
  • the silicon carbide-based sintered body of the present embodiment is a silicon carbide-based sintered body having silicon carbide particles as a main component and a relative density of 95% or more.
  • the area is This is a silicon carbide based sintered body in which coarse granular silicon carbide particles 1b of 170 ⁇ m 2 or more exist in an area of 6 to 15 area%.
  • coarse granular silicon carbide particles 1b having an area of 170 ⁇ m 2 or more and fine granular silicon carbide particles 1a having a crystal grain size of 8 ⁇ m or less.
  • silicon carbide particles having a crystal grain size of more than 8 ⁇ m and an area of less than 170 ⁇ m 2 may exist.
  • the silicon carbide based sintered body of the present embodiment has fine silicon carbide particles 1a having a crystal grain size of 8 ⁇ m or less as a matrix and a relative density of 95% or more.
  • the presence of 6 to 15 area% of coarse granular silicon carbide particles 1b having an area of 170 ⁇ m 2 or more allows the coarse granular silicon carbide particles 1b to be used even if fine cracks occur due to thermal shock or mechanical shock. Since the progress of cracks can be suppressed, the mechanical properties such as strength and rigidity are excellent, and the thermal shock resistance is also excellent.
  • the apparent density of the silicon carbide sintered body is obtained in accordance with JIS R 1634-1998, and this apparent density is calculated as the theoretical density of the silicon carbide sintered body. It can be obtained by dividing by.
  • the theoretical density of the silicon carbide sintered body is determined by ICP (Inductively Coupled Plasma) emission spectroscopy or fluorescent X-ray analysis for each content of h constituting the silicon carbide sintered body. Component identification is performed by X-ray diffraction using CuK ⁇ rays.
  • the identified component is SiC or B 4 C
  • the content of Si and B determined by ICP emission spectroscopy or fluorescent X-ray analysis It is converted into SiC or B 4 C using the value of the amount.
  • the amount of carbon (excluding free carbon) in the silicon carbide sintered body is obtained by carbon analysis. The value obtained by subtracting the amount of carbon necessary for the Si or B carbide conversion from the amount of carbon in the silicon carbide sintered body obtained here may be used as the graphite content.
  • the components constituting the silicon carbide sintered body are, for example, silicon carbide and graphite, and the contents thereof are a mass% and b mass%, respectively, the theoretical densities of silicon carbide and graphite
  • the silicon carbide sintered material is calculated using the formula (1).
  • the theoretical density (TD) of the body was 3.08 g / cm 3
  • the apparent density of the silicon carbide sintered body determined in accordance with JIS R 1634-1998 was calculated as the theoretical density (TD) of 3.08.
  • the relative density can be determined by dividing by g / cm 3 .
  • the surface of the silicon carbide sintered body is ground using a cup-type grindstone made of diamond, and subsequently, a lap made of tin is used. Polishing is performed with diamond abrasive grains having a particle size of 1 to 3 ⁇ m until the arithmetic average height Ra specified by JIS B 0601-2001 (ISO 4287-1997) is 0.01 ⁇ m or less.
  • the silicon carbide sintered body is immersed in a heated and melted solution of sodium hydroxide and potassium nitrate in a mass ratio of 1: 1 for 20 seconds, and the polished surface is etched.
  • this etched surface is observed with an optical microscope at a magnification of 500 times, and a surface on which silicon carbide particles of various sizes are observed on average is defined as an observation surface in the present embodiment.
  • the surface on which silicon carbide particles of various sizes are observed on average is a region where the area of one particle exceeding 15000 ⁇ m 2 that is not observed in other regions, or the area is 170 ⁇ m. Rather than deliberately selecting a region free of two or more particles, it refers to a place where the coarse silicon carbide particles 1b and the fine silicon carbide particles 1a are present on average by observing a wide area of the etched surface. .
  • the area ratio (area%) of the coarse-grained silicon carbide particles 1b on the observation surface is determined by using image analysis software “A Image-kun” (registered trademark, manufactured by Asahi Kasei Engineering Co., Ltd.) using an image obtained by photographing the observation surface. This is done by applying a method called particle analysis.
  • the threshold value which is an index indicating the density of an image
  • the threshold value is set to 150
  • the total area of the extracted coarse granular silicon carbide particles 1b having an extracted area of 170 ⁇ m 2 or more is the area of the observation surface, for example, 0.054 mm 2 (lateral direction (The length of 0.27 mm and the length in the vertical direction is 0.2 mm)
  • the value expressed as a percentage is the area ratio of the coarse silicon carbide particles 1b.
  • the main configuration means that the cumulative area of silicon carbide particles is 80 area% or more when the area of the observation surface is 100 area%.
  • the particles observed on the observation surface are silicon carbide particles by confirming the respective distributions of Si and C using a wavelength dispersion X-ray microanalyzer device (JXA-8600M type, manufactured by JEOL Ltd.) When the Si and C distributions are overlapped, they can be confirmed by their overlapping.
  • 1A and 1B are partially enlarged photographs of images obtained by photographing the observation surface.
  • the coarse granular silicon carbide particles 1b have an average aspect ratio (major axis / minor axis) of 1 or more and 2 or less.
  • the average value of the aspect ratio of the coarse granular silicon carbide particles 1b is within this range, the crack progresses when a fine crack is generated by thermal shock or mechanical shock, as compared with the aspect ratio outside this range. Due to the suppression effect, a silicon carbide sintered body having further excellent mechanical properties such as strength and rigidity is obtained.
  • the major axis is the length of the longest portion of coarse granular silicon carbide particles 1b on the observation surface, and the minor axis is the length of the longest portion perpendicular to the major axis.
  • the average aspect ratio of coarse granular silicon carbide particles 1b can be obtained as follows. Coarse granular silicon carbide particles 1b having an area of 170 ⁇ m 2 or more extracted by particle analysis of image analysis software “A image-kun” (registered trademark, manufactured by Asahi Kasei Engineering Co., Ltd.) have a long diameter according to JIS R 1670-2006. And measure the minor axis. Then, the average value may be calculated after the aspect ratio of each coarse granular silicon carbide particle 1b is obtained by dividing the value of the major axis by the value of the minor axis.
  • the average crystal grain size of the silicon carbide particles is 2 ⁇ m or more and 6 ⁇ m or less. As described above, if the average crystal grain size of the silicon carbide particles is 2 ⁇ m or more and 6 ⁇ m or less, the coarse sintered silicon carbide particles 1b can be formed, but a dense sintered body can be obtained. Thus, a silicon carbide sintered body having excellent thermal conductivity can be obtained.
  • the average crystal grain size of the silicon carbide particles may be calculated using the same image as that used when obtaining the area ratio and aspect ratio of the coarse silicon carbide particles 1b. Specifically, with respect to an arbitrary point in the image, six straight lines each having a length of, for example, 168 ⁇ m are drawn at 30 ° intervals, and crystals existing on the six straight lines are drawn. It can be obtained by dividing the number by the total length of these straight lines.
  • the thermal conductivity is confirmed by the thermal conductivity (W / (m ⁇ K)) measured according to JIS R 1601-2008 (ISO 14704-2000 (MOD)).
  • coarse granular silicon carbide particles 1b contain calcium. Since calcium has a linear expansion coefficient different from that of silicon carbide forming coarse granular silicon carbide particles 1b, when coarse granular silicon carbide particles 1b contain calcium, coarse granular silicon carbide particles 1b have a difference due to the difference in linear expansion coefficient. Residual stress is generated inside. And since the compressive stress has arisen in the grain boundary of the coarse granular silicon carbide particle 1b and the adjacent fine granular silicon carbide particle 1a etc.
  • the fracture toughness may be measured in accordance with a precracking fracture test method (SEPB method) defined in JIS R 1607-2010 (ISO 15732-2003 (MOD)).
  • the content of calcium should be 0.1% by mass or less with respect to 100% by mass of the silicon carbide sintered body.
  • the calcium content may be determined using ICP emission spectroscopy.
  • the coarse granular silicon carbide particles 1b contain calcium is confirmed by using a wavelength dispersive X-ray microanalyzer (JXA-8600M type manufactured by JEOL Ltd.) to confirm the calcium distribution. This can be confirmed by the presence or absence of calcium at the location corresponding to the silicon carbide particles 1b.
  • JXA-8600M type manufactured by JEOL Ltd. a wavelength dispersive X-ray microanalyzer
  • the silicon carbide sintered body of the present embodiment has an oxygen content of 1.5% by mass or less.
  • the oxygen content is 1.5% by mass or less, the formation of an amorphous phase in the grain boundary phase is reduced if the silicon carbide sintered body is formed by liquid phase sintering. Can be increased.
  • the oxygen content may be obtained by an oxygen analysis method.
  • the silicon carbide based sintered body of the present embodiment contains graphite, and the content of this graphite is preferably 10% by mass or less.
  • Graphite has a lower hardness than silicon carbide and easily wears out, but it has a high lubricating action, so it can maintain good sliding characteristics.
  • wear can be suppressed and good sliding characteristics can be maintained due to the high lubricating action of graphite. it can.
  • what is necessary is just to perform with the method shown when calculating
  • the graphite contained in the silicon carbide based sintered body of the present embodiment has an average crystal grain size of 4 ⁇ m or more and 43 ⁇ m or less.
  • the average crystal grain size of graphite is 4 ⁇ m or more and 43 ⁇ m or less, wear can be suppressed and high sealing performance can be maintained, and grain growth of silicon carbide crystal particles can be promoted during the sintering process. Thus, a denser silicon carbide sintered body can be obtained.
  • graphite preferably has an average crystal grain size of 12 ⁇ m to 30 ⁇ m.
  • about the average crystal grain size of graphite about 10 pieces of graphite are extracted using the same image as when obtaining the area ratio and aspect ratio of coarse granular silicon carbide particles 1b, and in accordance with JIS R 1670-2006.
  • the major axis and the minor axis are measured, the arithmetic mean is regarded as the crystal grain size of each graphite, and the average of the values excluding the maximum and minimum values of these crystal grain sizes is regarded as the average crystal grain size of graphite. do it.
  • FIG. 2 is a schematic diagram showing an example of the crystal structure of graphite.
  • the crystal structure of graphite is a structure in which the carbon layer surface shows an orderly orientation as shown in FIG. 2, the pores in the crystal grains of graphite are reduced, so that the compressive strength of the silicon carbide based sintered body is increased. can do.
  • the graphite has a half-value width of a diffraction peak from the (002) plane measured by the X-ray diffraction method of 0.3 ° or less (excluding 0 °).
  • the crystal structure of graphite can be made into a dense structure, so that mechanical properties such as compressive strength, such as bending strength, static elastic modulus and hardness are increased. can do.
  • the crystal structure of graphite is preferably a hexagonal crystal structure called 2H graphite.
  • the sliding component of the present embodiment is formed by polishing the surface of the silicon carbide sintered body of the present embodiment, the effect of suppressing the progress of cracks when a fine crack is generated by thermal shock, Along with excellent mechanical properties such as strength and rigidity, and excellent thermal shock resistance, it can withstand long-term use as a sliding component.
  • FIG. 3A is a partial cross-sectional view showing an example of a mechanical seal in which the sliding component of this embodiment is applied to a mechanical seal ring
  • FIG. 3B is a perspective view of the mechanical seal ring shown in FIG.
  • This mechanical seal has a mechanical seal ring 5 which exerts a sealing action by sliding a sliding surface 15b of a movable member 5b which is an annular body having a convex portion on a sliding surface 15a of a fixed member 5a which is an annular body. It is an apparatus provided with.
  • the mechanical seal ring 5 is attached between a rotating shaft 6 that transmits a driving force by a driving mechanism (not shown) and a casing 7 that rotatably supports the rotating shaft 6, and includes a fixed member 5a and a movable member 5b.
  • the mutual sliding surfaces 15a and 15b are installed so as to form a vertical surface with respect to the rotating shaft 6.
  • the movable member 5b is buffered by the packing 8, and a coil spring 9 is installed on the side of the packing 8 facing the movable member 5b so as to wind the rotating shaft 6.
  • a coil spring 9 is installed on the side of the packing 8 facing the movable member 5b so as to wind the rotating shaft 6.
  • the fixed member 5a that is in contact with the movable member 5b through the sliding surface 15b and the sliding surface 15a is supported by a shock absorbing rubber 12, and the shock absorbing rubber 12 is placed inside the casing 7 that is an outer frame of the mechanical seal. It is attached and supports the fixing member 5a.
  • the buffer rubber 12 and the packing 8 also have a function of absorbing vibration generated by the rotation of the rotating shaft 6.
  • the fluid 14 penetrates to the inside surrounded by the casing 7 of the mechanical seal, but the sealing action by the O-ring 13 provided between the packing 8 and the rotating shaft 6 and the sliding of the mechanical seal ring 5 are performed.
  • the fluid 14 is prevented from leaking from the mechanical seal to the outside by the sealing action of the surfaces 15a and 15b.
  • a part of the fluid 14 enters between the sliding surfaces 15a and 15b of the mechanical seal ring 5 and acts as a lubricating liquid.
  • the fixed member 5a is a flat ring-shaped body
  • the movable member 5b is a ring-shaped body having a convex portion.
  • the fixed member 5a is a ring-shaped body having a convex portion.
  • the movable member 5b can be a flat annular body.
  • the mechanical seal ring 5 is composed of a fixed member 5a and a movable member 5b that slide with the sliding surfaces 15a and 15b coming into contact with each other via a lubricant.
  • the fixed member 5a and the movable member 5b are slid. At least one of these preferably uses a sliding component made of the silicon carbide sintered body of the present embodiment.
  • the mechanical seal provided with the mechanical seal ring 5 made of the sliding parts of the present embodiment has a low replacement frequency and can be used continuously for a long period of time, the operation efficiency is high. Easy maintenance.
  • FIG. 4A and 4B show an example of a forceset valve provided with the sliding component of the present embodiment, in which FIG. 4A is a perspective view with the fluid passage opened, and FIG. 4B is a perspective view with the fluid passage closed.
  • FIG. 4A is a perspective view with the fluid passage opened
  • FIG. 4B is a perspective view with the fluid passage closed.
  • the facet valve 16 includes a substrate-like fixed valve body 17 and a rotary valve body 18 that slide against each other with the sliding surfaces 17a and 18a in contact with each other via a lubricating liquid.
  • the fixed valve body 17 is fixed to a resin case (not shown), and the movable valve body 18 is configured to move on the fixed valve body 17 inside the resin case.
  • Fluid passages 17b and 18b are formed in the thickness direction in the fixed valve body 17 and the movable valve body 18, respectively, and both fluid passages 17b and 18b are connected on the sliding surfaces 17a and 18a.
  • a lever 19 is fixed to the movable valve body 18, and the movable valve body 18 is moved by moving the lever 19 in the vertical direction or the rotational direction.
  • the fixed valve body 17 corresponds to a fixed member
  • the movable valve body 18 corresponds to a movable member.
  • fluid such as water and hot water sequentially flows from the direction of the white arrow to the fluid passages 17b and 18b and is connected to the force valve 16.
  • the fluid is discharged from the faucet (not shown).
  • the fluid inserted between the sliding surfaces 17a and 18a together with the silicon grease previously applied to one of the sliding surfaces 17a and 18a serves as a lubricating liquid and acts to maintain the sliding characteristics.
  • the lever 19 can move the movable valve body 18 in either the vertical direction to close the fluid passages 17b, 18b, thereby stopping the discharge of fluid from the faucet. be able to. Moreover, since the area of the end surface to which the fluid passages 17b and 18b are connected is adjusted by moving the movable valve body 18 in the rotation direction, the flow rate of the fluid discharged from the faucet can be adjusted.
  • At least one of the fixed valve body 17 and the movable valve body 18 uses a sliding component made of the silicon carbide sintered body of this embodiment.
  • the sliding part made of the silicon carbide sintered body of the present embodiment for at least one of the fixed valve body 17 and the movable valve body 18, in addition to excellent wear resistance, finer by long-term use. Even if cracks occur, the progress of cracks is suppressed by coarse granular silicon carbide particles 1b, so that good sliding characteristics can be maintained.
  • the frequency of parts replacement is low, it can be used continuously over a long period of time.
  • FIG. 5 shows a rolling bearing which is an example of a rolling support device provided with the sliding component of the present embodiment, (a) is a cross-sectional view, and (b) shows a cage of the rolling bearing shown in (a). It is a perspective view shown.
  • the rolling bearing 20 in the example shown in FIG. 5A includes a first member (outer ring) 21 and a second member (inner ring) 22 provided with raceway surfaces 21a and 22a arranged to face each other. And a plurality of rolling elements 23 that are rotatably arranged between the raceway surfaces 21a and 22a. When the rolling elements 23 roll, one of the first member 21 and the second member 22 is in relation to the other. It is configured to move relative to each other.
  • a counter bore 22b is formed on one side of the rolling element 23 on the raceway surface of the second member 22 so as to be inclined from the raceway surface 22a of the second member 22.
  • the counter bore 22b is for facilitating the attachment of the rolling element 23 between the first member 21 and the second member 22.
  • the cage 24 shown in FIG. 5 (b) has an annular shape, and holds the rolling elements 23 by pockets 24a arranged at equal intervals in the circumferential direction.
  • the first member 21 or the second member 22 and the rolling element 23 correspond to a fixed member and a movable member, respectively, and the first member 21, the second member 22 and At least one of the rolling elements 23 preferably uses a sliding component made of the silicon carbide sintered body of this embodiment.
  • the sliding component made of the silicon carbide sintered body of this embodiment as at least one of the first member 21, the second member 22, and the rolling element 23, even if a fine crack is generated due to thermal shock, it is rough. Since the progress of cracks is suppressed by the granular silicon carbide particles 1b, good sliding characteristics can be maintained. In addition, since the frequency of parts replacement is low, it can be used continuously over a long period of time.
  • the arithmetic average height (Ra) is preferably 0.6 ⁇ m or less.
  • the surface of the rolling element 23 preferably has an arithmetic average height (Ra) of 0.01 ⁇ m or less.
  • the cage 24 is mainly composed of polyetheretherketone (PEEK), polyamideimide alloy (PAI) or thermoplastic polyimide (TPI), and includes aluminum borate whisker, potassium titanate whisker, barium titanate whisker, and titanium oxide. It is preferable to include fibrous fillers such as whiskers, carbon whiskers, graphite whiskers, silicon carbide whiskers, silicon nitride whiskers, and aluminum oxide whiskers. By including such a fibrous filler, the cage 24 can increase its mechanical strength, wear resistance and dimensional stability.
  • PEEK polyetheretherketone
  • PAI polyamideimide alloy
  • TPI thermoplastic polyimide
  • fibrous fillers such as whiskers, carbon whiskers, graphite whiskers, silicon carbide whiskers, silicon nitride whiskers, and aluminum oxide whiskers.
  • the surface of the silicon carbide sintered body is polished more than the inside of the silicon carbide sintered body. It is preferable that a large amount of graphite is present on the sliding surface. Thereby, the sliding characteristics can be further enhanced by the lubricating action of graphite while maintaining the mechanical characteristics.
  • the inside of the silicon carbide sintered body is the center of the thickness of the silicon carbide sintered body, and is formed by polishing the inside of the silicon carbide sintered body and the surface of the silicon carbide sintered body.
  • the difference in the graphite content from the sliding surface is preferably 2% by mass or more.
  • the protective body of the present embodiment uses the silicon carbide sintered body of the present embodiment, so that the strength and rigidity of the protective body can be reduced due to the effect of suppressing the progress of cracks when a fine crack is generated by mechanical impact. Therefore, it can be suitably used as a protective body.
  • This protective body is, for example, a substrate having a vertical and horizontal length of 40 mm or more and 60 mm or less and a thickness of 6 mm or more and 12 mm or less, and is mounted on an automobile, a train, a helicopter, a jet plane, etc. It is.
  • the protective body of the present embodiment has a dynamic elastic modulus of 426 GPa or more.
  • the dynamic elastic modulus is 426 GPa or more, the ability to deform the flying object that applies an impact to the protective body is increased, and therefore the impact of the flying object can be instantaneously dispersed.
  • the dynamic elastic modulus may be obtained in accordance with an ultrasonic pulse method based on JIS R 1602-1995, and the dynamic elastic modulus is more preferably 430 GPa or more.
  • the silicon carbide based sintered body of the present embodiment first, coarse granular powder and fine granular powder are prepared as silicon carbide powder, and water and, if necessary, a dispersant are added by a ball mill or a bead mill. Grind and mix for ⁇ 60 hours to make slurry.
  • the ranges of the particle sizes of the fine and coarse granular powders after pulverization and mixing are 0.4 ⁇ m or more and 4 ⁇ m or less, and 11 ⁇ m or more and 34 ⁇ m or less.
  • the obtained slurry is made of graphite powder, a dispersant for dispersing the graphite powder (hereinafter referred to as a dispersant for graphite), boron carbide powder and amorphous carbon powder or phenol resin.
  • a dispersant for graphite a dispersant for graphite
  • boron carbide powder a dispersant for graphite
  • amorphous carbon powder or phenol resin a sintering aid and a binder
  • granules whose main component is silicon carbide are obtained by spray drying.
  • fine granular powder is 6 mass% or more and 15 mass% or less, for example, coarse granular powder is 85 mass% or more and 94 mass% or less.
  • coarse granular powder is 85 mass% or more and 94 mass% or less.
  • the coarse granular powder whose average value of the aspect ratio is 1 or more and 1.6 or less in advance. May be used.
  • the addition amount of graphite powder and the addition amount of amorphous carbon powder as a sintering aid It is sufficient that the sum of 1 ⁇ 2 and 10% is 10% by mass or less with respect to 100% by mass of the silicon carbide powder.
  • graphite powder having an average particle size of 8 ⁇ m or more and 48 ⁇ m or less may be used.
  • a graphite dispersant by using a graphite dispersant, it can be adsorbed to a hydrophobic graphite powder and wetted and permeated into a slurry using water as a solvent, and acts to suppress aggregation of graphite. Homogeneous granules containing graphite can be obtained.
  • an anionic surfactant such as carboxylate such as sodium polycarboxylate, sulfonate, sulfate ester salt and phosphate ester salt.
  • the anionic surfactant which is a graphite dispersant
  • the graphite powder When the anionic surfactant, which is a graphite dispersant, is adsorbed to the graphite powder, the graphite powder easily wets and penetrates into the slurry, and the repulsion of the graphite powder is caused by the charge repulsion of the hydrophilic group of the anionic surfactant. Since aggregation is suppressed, the graphite powder can be sufficiently dispersed without agglomerating in the slurry.
  • the carbon that is a component of the sintering aid is free carbon and is present in at least one of the open pores and the grain boundary phase on the sliding surface of the sliding component, and when the sliding component slides, The free carbon easily flows out on the sliding surface that comes into contact with the free carbon and is contained in the lubricating liquid.
  • the sliding characteristics of the sliding component can be improved.
  • the granules are filled into a predetermined mold and pressed and molded from the thickness direction at a pressure appropriately selected in the range of 49 to 147 MPa to obtain molded bodies that are precursors of the fixed member and the movable member, respectively.
  • Each of the obtained molded bodies is degreased in a nitrogen atmosphere at a temperature of 450 to 650 ° C. and a holding time of 2 to 10 hours to obtain a degreased body.
  • the degreased body is placed in a firing furnace, and held at a maximum temperature of 1800 to 2200 ° C. and a holding time of 3 to 6 hours in a reduced-pressure atmosphere of an inert gas.
  • a sintered body can be obtained.
  • it does not specifically limit about an inert gas Since acquisition and handling are easy, it is suitable to use argon gas.
  • the average crystal grain size of the silicon carbide particles in the silicon carbide sintered body can be adjusted by setting the maximum temperature so as to be 2 ⁇ m or more and 6 ⁇ m or less. Further, when the silicon carbide sintered body is used as a sliding part, there is more graphite on the sliding surface obtained by polishing the surface of the silicon carbide sintered body than inside the silicon carbide sintered body.
  • the reduced pressure atmosphere of the inert gas may be changed to a vacuum atmosphere, and the holding may be performed by holding at the same temperature as the above temperature and at the same holding time as the holding time.
  • the obtained silicon carbide sintered body of the present embodiment may be subjected to processing such as grinding or polishing on each main surface as necessary.
  • processing such as grinding or polishing on each main surface as necessary.
  • the surface may be polished with a tin lapping machine so that the arithmetic average height (Ra) is 0.98 ⁇ m or less.
  • Ra arithmetic average height
  • the arithmetic average height (Ra) may be measured in accordance with JIS B 0601-2001 (ISO 4287-1997), and the measurement length and the cut-off value are 5 mm and 0.8 mm, respectively. If the surface roughness meter is used, for example, a stylus having a stylus tip radius of 2 ⁇ m is applied to the sliding surface of the sliding component, and the scanning speed of the stylus is 0.5 mm / second. That's fine.
  • the silicon carbide sintered body of the present embodiment obtained by the manufacturing method described above is a silicon carbide sintered body mainly composed of silicon carbide particles and having a relative density of 95% or more. Coarse granular silicon carbide particles with an area of 170 ⁇ m 2 or more on the surface of the body are present in an area of 6 to 15 area%, even if fine cracks are generated due to thermal shock or mechanical shock. Since the progress of cracks is suppressed by the silicon carbide particles, a silicon carbide sintered body having excellent thermal shock resistance as well as mechanical properties such as strength and rigidity is obtained.
  • the sliding component obtained by polishing the surface of the silicon carbide based sintered body of the present embodiment can maintain good sliding characteristics over a long period of time, and therefore can be suitably used for a mechanical seal ring. Moreover, it can be used suitably also for sliding parts, such as a forceset valve and a rolling support apparatus. Moreover, it can be used suitably also as a protective body.
  • a silicon carbide powder fine and coarse powders, water, and a dispersant for dispersing these silicon carbide powders were added, placed in a ball mill, and pulverized and mixed for 48 hours to obtain a slurry.
  • boron carbide powder and amorphous carbon powder carbon black and binder as a sintering aid were added and pulverized and mixed, and then spray-dried so that the main component was silicon carbide.
  • Granules having a particle size of 80 ⁇ m were obtained.
  • some samples were further mixed with graphite powder and sodium polycarboxylate as a graphite dispersant, and then spray-dried in the same manner to contain the main component.
  • Granules of silicon carbide having an average particle size of 80 ⁇ m were obtained.
  • the mass ratios of the fine powder and coarse powder of the silicon carbide powder as the main component are as shown in Table 1, and the respective particle sizes after pulverization and mixing are 0.4 ⁇ m or more and 4 ⁇ m or less, 11 ⁇ m or more and 34 ⁇ m or less. Met. Further, the average value of the aspect ratio of the coarse granular powder, the addition amount of the sintering aid, the average particle size and the addition amount of the graphite powder were as shown in Table 1, respectively.
  • the respective particle sizes after pulverization and mixing of the fine granular powder and coarse granular powder and the average particle diameter of the graphite powder were determined in accordance with JIS R 1629-1997. Moreover, about the sample which added the graphite powder, 4 mass parts of addition amount of sodium polycarboxylate was added with respect to 100 mass parts of graphite powder as a dispersing agent for graphite.
  • the obtained granule is filled into a mold and molded by applying a pressure of 98 MPa from the thickness direction, and the obtained molded body is heated in a nitrogen atmosphere for 20 hours and held at 600 ° C. for 5 hours. Then, it was naturally cooled and degreased to obtain a degreased body. Next, the degreased body was fired in a reduced pressure atmosphere of argon gas at the firing temperature shown in Table 1 for 5 hours to obtain a silicon carbide based sintered body.
  • the four-point bending strength, dynamic elastic modulus, and critical temperature difference were each measured according to JIS R. It was measured according to 1601-2008 (ISO 14704-2000 (MOD)), ultrasonic pulse method based on JIS R 1602-1995, and precision method based on JIS R 1648-2002. These measured values are shown in Table 2.
  • the defatted body is fired in a reduced pressure atmosphere of argon gas at the firing temperature shown in Table 1 for 5 hours, thereby firing the silicon carbide-based fired body which is a ring-shaped body having a plate-like annular body and convex portions.
  • a ligature was obtained.
  • each silicon carbide sintered body was ground with a surface grinder, and polished with an alumina lapping machine using diamond abrasive grains having an average particle diameter of 3 ⁇ m.
  • the arithmetic average height (Ra) is polished with a tin lapping machine so that the arithmetic average height (Ra) is 0.98 ⁇ m or less to form a sliding surface.
  • the fixing members 5a having a thickness of 3 mm and a thickness of 25 mm and 16 mm, respectively, were obtained.
  • a movable member 5b having a convex portion and having an outer diameter and an inner diameter of 25 mm and 16 mm, respectively, and a thickness of 7 mm was obtained.
  • the fixing member 5a prepared using the granules of No. 12 and the sample No.
  • the following sliding test was conducted using the movable member 5b produced using the granules 1 to 23. Specifically, the sliding surfaces 15a and 15b of the fixed member 5a and the movable member 5b were brought into contact with each other and slid under the following sliding conditions.
  • ⁇ Sliding conditions> ⁇ Relative speed: 8m / sec ⁇ Surface pressure: 400kPa Lubricating liquid: water
  • the relative speed is the rotational speed of the movable member 5b with respect to the fixed member 5a at a position (hereinafter referred to as position P) that is 11.25 mm away from the center of the rotating shaft toward the outer peripheral side.
  • the surface pressure is a pressure per unit area of the movable member 5b with respect to the fixed member 5a, and a predetermined pressure F for bringing the fixed member 5a and the movable member 5b into contact with each other is a sliding surface 15b of the movable member 5b.
  • the area was calculated by measuring the outer diameter and the inner diameter of the convex portion of the movable member 5b with a gauge using an optical microscope equipped with a gauge for measuring dimensions at a magnification of 50 times. .
  • the thickness of the movable member 5b was measured with the dial cage before starting sliding and 150 hours after starting sliding, and the difference in thickness was defined as the wear depth.
  • Table 2 shows the coefficient of friction and the wear depth.
  • JIS B 0601-2001 is used with diamond abrasive grains having a particle diameter of 1 to 3 ⁇ m using a lapping machine made of tin. Polishing was performed until the arithmetic average height (Ra) specified by (ISO 4287-1997) was 0.01 ⁇ m or less.
  • Ra arithmetic average height
  • the silicon carbide sintered body was immersed in a heated and melted solution of sodium hydroxide and potassium nitrate in a mass ratio of 1: 1 for 20 seconds, and the polished surface was etched.
  • the major axis value is divided by the minor axis value.
  • the average value was calculated. Table 2 shows the average values of the area ratio and aspect ratio of coarse granular silicon carbide particles 1b.
  • the graphite contained in the movable member 5b was identified by the X-ray diffraction method using CuK ⁇ rays.
  • the amount of carbon in the silicon carbide sintered body was determined by carbon analysis, and the content of Si and B was determined by ICP emission spectroscopic analysis. Then, using the value of the content of Si and B in terms of SiC and B 4 C is a carbide, graphite by subtracting the amount of carbon needed for this carbide conversion of carbon content in the silicon carbide sintered body It was set as content.
  • sample No. No. 1 has a low firing temperature and a relative density of less than 95%, so the wear depth is large and it is easy to wear, so it cannot withstand long-term use as a sliding part.
  • Sample No. In No. 2 since coarse silicon carbide particles 1b do not exist in an area of 6 area% or more, it was found that the value of the critical temperature difference is small and the progress of cracks caused by thermal shock cannot be sufficiently suppressed.
  • Sample No. In No. 23 since the coarse-grained silicon carbide particles 1b were present exceeding 15 area%, the values of the four-point bending strength and the dynamic elastic modulus were low.
  • Sample No. Nos. 3 to 22 have a relative density of 95% or more, and there are 6 to 15 area% of coarse granular silicon carbide particles having an area of 170 ⁇ m 2 or more on the observation surface. Since the value of the elastic modulus is large and the value of the critical temperature difference indicating thermal shock resistance is large, even if fine cracks are generated due to thermal shock or mechanical shock, the progress of cracks is suppressed by the coarse granular silicon carbide particles 1b. It can be said that this is a silicon carbide-based sintered body capable of forming.
  • sample Nos. Differing only in the average aspect ratio of the coarse granular powder.
  • sample no. In Nos. 18 and 19, since the average aspect ratio of coarse-grained silicon carbide particles 1b is 1 or more and 2 or less, Sample No. It was found that the 4-point bending strength and the dynamic elastic modulus were larger than 20, and the mechanical properties were excellent.
  • Sample No. 9 to 17 contain graphite, so the friction coefficient is low and it can be seen that graphite has a high lubricating action, but the result of wear depth indicates that the graphite content is 10% by mass or less. Can be said to be suitable.
  • the silicon carbide based sintered body of the present embodiment can suppress the progress of cracks with coarse granular silicon carbide particles even if fine cracks are generated due to thermal shock or mechanical shock. It was found that it has excellent thermal shock resistance as well as mechanical properties such as rigidity. Therefore, the sliding component formed by polishing the surface of the silicon carbide sintered body of the present embodiment can maintain good sliding characteristics over a long period of time, and therefore can be suitably used for a mechanical seal ring. I understood. Moreover, it turned out that it can be used suitably also for sliding parts, such as a faucet valve and a rolling support apparatus. Moreover, it turned out that it can be used suitably also as a protective body.
  • Example 1 As in Example 1, a fine powder and coarse granular powder were used as silicon carbide powder, the mass ratio was 90:10, water and a dispersant for dispersing these silicon carbide powders were added, and a ball mill was added. The mixture was pulverized and mixed at different times for pulverization and mixing to obtain a slurry. Then, after adding boron carbide powder, carbon black which is an amorphous carbon powder, and a binder, mixing, and then spray drying, granules whose main component is silicon carbide and whose average particle size is 80 ⁇ m Got. As addition amounts, silicon carbide powder was 99.1% by mass, boron carbide was 0.4% by mass, and carbon black was 0.5% by mass. Next, by using the obtained granules, a silicon nitride sintered body was obtained by the same production method as in Example 1. The maximum temperature was the temperature shown in Table 3.
  • the thermal conductivity and the four-point bending strength are measured according to JIS R 1611-2010 (ISO 18755-2005 (MOD)) and JIS R 1601-2008 (ISO 14704-2000 (MOD)).
  • each sample was subjected to processing such as polishing and etching in the same manner as in Example 1, and the observation surface was imaged with an optical microscope at a magnification of 500 times, with an arbitrary point in the image as the center, Each straight line having a length of 168 ⁇ m was drawn at 30 ° intervals, and the number of crystals existing on the six straight lines was divided by the total length of these straight lines.
  • Table 3 shows the measured values of the average crystal grain size, thermal conductivity, and 4-point bending strength of the silicon carbide particles.
  • sample No. Nos. 25 to 28 have large values of thermal conductivity and 4-point bending strength, and the average crystal grain size of silicon carbide particles is 2 ⁇ m or more and 6 ⁇ m or less. It turned out to be a ligation.
  • Sample No. of Example 2 A silicon carbide sintered body was obtained by the same production method as that for producing 28. Sample No. For 31 and 32, calcium was added when boron carbide or the like was added.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • General Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Products (AREA)
  • Mechanical Sealing (AREA)

Abstract

L'invention concerne un corps fritté de carbure de silicium et un composant de glissement l'utilisant, et un corps protecteur, qui même si de fines fissures se produisent dues à un choc thermique ou à un impact mécanique, sont capables d'inhiber le développement des fissures sur une durée prolongée. Le corps fritté en carbure de silicium est configuré principalement à partir de particules de silicium et possède une densité relative de 95 % ou plus. Sur une surface d'observation du corps fritté de carbure de silicium, des particules de carbure de silicium à grains grossiers (1b) de 170 µm² d'aire de surface ou plus représentent entre 6 % à 15 % inclus de l'aire de surface. Le corps fritté en carbure de silicium présente d'excellentes propriétés mécaniques telles que la résistance et la rigidité, et même lorsque de fines fissures se produisent dues au choc thermique ou à un impact mécanique, les particules de carbure de silicium à grains grossiers (1b) sont capables d'inhiber le développement des fissures.
PCT/JP2011/054150 2010-02-24 2011-02-24 Corps fritté en carbure de silicium et composant de glissement l'utilisant, et corps protecteur WO2011105490A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US13/581,171 US9388083B2 (en) 2010-02-24 2011-02-24 Silicon carbide sintered body and sliding component using the same, and protective body
JP2012501846A JP5597693B2 (ja) 2010-02-24 2011-02-24 炭化珪素質焼結体およびこれを用いた摺動部品ならびに対飛翔体用防護体
EP11747450.2A EP2540688B1 (fr) 2010-02-24 2011-02-24 Corps fritté en carbure de silicium et composant de glissement l'utilisant, et corps protecteur
CN201180010704.1A CN102770394B (zh) 2010-02-24 2011-02-24 碳化硅质烧结体及使用其的滑动部件以及防护体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010-038947 2010-02-24
JP2010038947 2010-02-24

Publications (1)

Publication Number Publication Date
WO2011105490A1 true WO2011105490A1 (fr) 2011-09-01

Family

ID=44506891

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/054150 WO2011105490A1 (fr) 2010-02-24 2011-02-24 Corps fritté en carbure de silicium et composant de glissement l'utilisant, et corps protecteur

Country Status (5)

Country Link
US (1) US9388083B2 (fr)
EP (1) EP2540688B1 (fr)
JP (1) JP5597693B2 (fr)
CN (1) CN102770394B (fr)
WO (1) WO2011105490A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014126191A (ja) * 2012-12-27 2014-07-07 Kyocera Corp 回転継手
JP2016204221A (ja) * 2015-04-24 2016-12-08 京セラ株式会社 炭化珪素質焼結体およびこれを用いた摺動部材、ならびにフォーセットバルブ
JP2017515057A (ja) * 2014-03-21 2017-06-08 イーグルブルクマン ジャーマニー ゲセルシャフト ミト ベシュレンクテル ハフツング ウント コンパニー コマンディトゲゼルシャフト グラフェン含有スライドリング

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6251381B2 (ja) * 2014-03-25 2017-12-20 京セラ株式会社 流路部材および半導体モジュール
US11387132B2 (en) * 2016-01-27 2022-07-12 Sumitomo Osaka Cement Co., Ltd. Ceramic material and electrostatic chuck device
CN106402391A (zh) * 2016-11-07 2017-02-15 宁波欧翔精细陶瓷技术有限公司 一种机械密封用碳化硅烧结材料以及使用该材料的机械密封装置
JP7025969B2 (ja) * 2018-03-26 2022-02-25 日本碍子株式会社 多孔質材料、セル構造体および多孔質材料の製造方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6212667A (ja) * 1985-07-09 1987-01-21 東芝セラミツクス株式会社 半導体用部材の製造方法
JP2002326873A (ja) * 2001-03-08 2002-11-12 Wacker Chemie Gmbh セラミック複合材料、その製造方法および使用
JP2003077964A (ja) * 2001-08-31 2003-03-14 Ibiden Co Ltd ウエハプローバ用チャックトップ
JP2003095744A (ja) 2001-09-21 2003-04-03 Nippon Tungsten Co Ltd 炭化珪素焼結体及びそれを用いた半導体製造用部材、磁気ヘッド製造用部材、耐摩耗摺動部材およびその製造方法
WO2005026074A1 (fr) * 2003-09-12 2005-03-24 Ibiden Co., Ltd. Comprimé en céramique frittée et filtre en céramique
JP2006278495A (ja) * 2005-03-28 2006-10-12 Fdk Corp 熱衝撃耐性フェライトコアの製造方法
JP2007321797A (ja) * 2006-05-30 2007-12-13 Kyocera Corp 摺動部材およびこれを用いたメカニカルシールリング
WO2009016861A1 (fr) * 2007-07-30 2009-02-05 Kyocera Corporation Élément protecteur et appareil protecteur utilisant celui-ci
JP2010006642A (ja) * 2008-06-27 2010-01-14 Kyocera Corp 摺動部材、弁体およびフォーセットバルブ

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3142359B2 (ja) 1992-03-23 2001-03-07 日本碍子株式会社 プレス成形方法
EP2138474B1 (fr) * 2008-06-23 2018-08-08 Imerys Kiln Furniture Hungary Ltd. Matériau sic

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6212667A (ja) * 1985-07-09 1987-01-21 東芝セラミツクス株式会社 半導体用部材の製造方法
JP2002326873A (ja) * 2001-03-08 2002-11-12 Wacker Chemie Gmbh セラミック複合材料、その製造方法および使用
JP2003077964A (ja) * 2001-08-31 2003-03-14 Ibiden Co Ltd ウエハプローバ用チャックトップ
JP2003095744A (ja) 2001-09-21 2003-04-03 Nippon Tungsten Co Ltd 炭化珪素焼結体及びそれを用いた半導体製造用部材、磁気ヘッド製造用部材、耐摩耗摺動部材およびその製造方法
WO2005026074A1 (fr) * 2003-09-12 2005-03-24 Ibiden Co., Ltd. Comprimé en céramique frittée et filtre en céramique
JP2006278495A (ja) * 2005-03-28 2006-10-12 Fdk Corp 熱衝撃耐性フェライトコアの製造方法
JP2007321797A (ja) * 2006-05-30 2007-12-13 Kyocera Corp 摺動部材およびこれを用いたメカニカルシールリング
WO2009016861A1 (fr) * 2007-07-30 2009-02-05 Kyocera Corporation Élément protecteur et appareil protecteur utilisant celui-ci
JP2010006642A (ja) * 2008-06-27 2010-01-14 Kyocera Corp 摺動部材、弁体およびフォーセットバルブ

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014126191A (ja) * 2012-12-27 2014-07-07 Kyocera Corp 回転継手
JP2017515057A (ja) * 2014-03-21 2017-06-08 イーグルブルクマン ジャーマニー ゲセルシャフト ミト ベシュレンクテル ハフツング ウント コンパニー コマンディトゲゼルシャフト グラフェン含有スライドリング
JP2016204221A (ja) * 2015-04-24 2016-12-08 京セラ株式会社 炭化珪素質焼結体およびこれを用いた摺動部材、ならびにフォーセットバルブ

Also Published As

Publication number Publication date
EP2540688A4 (fr) 2013-10-30
EP2540688A1 (fr) 2013-01-02
CN102770394A (zh) 2012-11-07
JPWO2011105490A1 (ja) 2013-06-20
US9388083B2 (en) 2016-07-12
JP5597693B2 (ja) 2014-10-01
CN102770394B (zh) 2014-12-31
EP2540688B1 (fr) 2019-03-20
US20120321853A1 (en) 2012-12-20

Similar Documents

Publication Publication Date Title
JP5597693B2 (ja) 炭化珪素質焼結体およびこれを用いた摺動部品ならびに対飛翔体用防護体
JP4854482B2 (ja) 炭化硼素質焼結体およびその製造方法
US8207077B2 (en) Abrasion-resistant sintered body, sliding member, and pump
JP5289464B2 (ja) 摺動部品およびこれを備えたメカニカルシール，フォーセットバルブならびに転がり支持装置
JP5314425B2 (ja) 摺動部材とその製造方法
JP2006036624A (ja) 摺動部材用多孔質セラミックスとその製造方法及びこれを用いたメカニカルシールリング
KR101217580B1 (ko) 슬라이딩 부재, 메커니컬 시일 링, 메커니컬 시일 및 포셋 밸브
JP5404495B2 (ja) 耐磨耗性部材およびこれを用いた転がり支持装置
JP2007084368A (ja) セラミックス摺動部材とその製造方法およびこれを用いたメカニカルシールリング用部材並びにメカニカルシールリング
JP2017024161A (ja) 研磨工具及びその製造方法並びに研磨物の製造方法
JP4741421B2 (ja) 摺動部材およびこれを用いたメカニカルシールリング
WO2015099148A1 (fr) Élément résistant à l'usure et dispositif support d'enroulement doté de celui-ci, et dispositif d'étanchéification d'arbre
Gutierrez-Mora et al. Influence of microstructure and crystallographic phases on the tribological properties of SiC obtained by spark plasma sintering
JP2007223890A (ja) 炭化けい素質焼結体とこれを用いた摺動部材およびメカニカルシールリング、並びにメカニカルシール
JP2018070413A (ja) 摺動部品およびフォーセットバルブ
WO2023054611A1 (fr) Matériau pour bille céramique, bille céramique, et procédé de production s'y rapportant
CN111356668A (zh) 氧化铝烧结体的前体、氧化铝烧结体的制造方法、磨粒的制造方法和氧化铝烧结体
JP6282943B2 (ja) 窒化珪素質焼結体およびこれを備える耐衝撃磨耗性部材
CN115485253B (zh) 耐磨损性构件以及使用了该耐磨损性构件的龙头阀、活塞-工作缸单元
JP2020099981A (ja) 砥粒を含む研削砥石の研削性の評価方法
JP2016050137A (ja) 窒化珪素質焼結体およびこれを備える耐磨耗性部材

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201180010704.1

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11747450

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2012501846

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 13581171

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 2011747450

Country of ref document: EP